Polyesters including isosorbide as a comonomer blended with other thermoplastic polymers

ABSTRACT

A polymer blend including a polyester and another thermoplastic polymer. The polyester includes terephthaloyl moieties and, optionally, other aromatic diacid moieties; and ethylene glycol moieties; optionally diethylene glycol moieties; isosorbide moieties; and, optionally one or more other diol moieties. The polyester has an inherent viscosity of at least about 0.35 dL/g.

RELATED APPLICATIONS

The following copending applications, filed on even date herewith, allcontain related subject matter: U.S. application Ser. Nos: 09/086,064;09/064,846; 09/064,719 and 09/064,720. The following issued patents, theapplications thereof having been filed on even date herewith, alsocontain related subject matter: U.S. Pat. No. 5,959,066 issued Sep. 28,1999; U.S. Pat. No. 5,958,581 issued Sep. 28, 1999; and U.S. Pat. No.6,025,061, issued Feb. 15, 2000. The contents of each of theabove-identified applications and patents is hereby incorporated byreference.

FIELD OF THE DISCLOSURE

This disclosure relates to polyester blends and methods of makingpolyester blends, and more specifically to polyesters containing anisosorbide moiety, blended with other thermoplastic polymers, andmethods of making them.

BACKGROUND OF THE DISCLOSURE

The diol 1,4:3,6-dianhydro-D-sorbitol, referred to hereinafter asisosorbide, the structure of which is illustrated below, is readily madefrom renewable resources, such as sugars and starches. For example,isosorbide can be made from D-glucose by hydrogenation followed byacid-catalyzed dehydration. ##STR1##

Isosorbide has been incorporated as a monomer into polyesters that alsoinclude terephthaloyl moieties. See, for example, R. Storbeck et al,Makromol.Chem., Vol.194, pp. 53-64 (1993); R. Storbeck et al, Polymer,Vol. 34, p. 5003 (1993). However, it is generally believed thatsecondary alcohols such as isosorbide have poor reactivity and aresensitive to acid-catalyzed reactions. See, for example, D. Braun etal., J. Prakt.Chem., Vol. 334, pp. 298-310 (1992). As a result of thepoor reactivity, polyesters made with an isosorbide monomer and estersof terephthalic acid are expected to have a relatively low molecularweight. Ballauff et al, Polyesters (Derived from Renewable Sources),Polymeric Materials Encyclopedia, Vol. 8, p. 5892 (1996).

Copolymers containing isosorbide moieties, ethylene glycol moieties, andterephthaloyl moieties have been reported only rarely. A copolymercontaining these three moieties, in which the mole ratio of ethyleneglycol to isosorbide was about 90:10, was reported in published GermanPatent Application No. 1,263,981 (1968). The polymer was used as a minorcomponent (about 10%) of a blend with polypropylene to improve thedyeability of polypropylene fiber. It was made by melt polymerization ofdimethyl terephthalate, ethylene glycol, and isosorbide, but theconditions, which were described only in general terms in thepublication, would not have given a polymer having a high molecularweight.

Copolymers of these same three monomers were described again recently,where it was observed that the glass transition temperature Tg of thecopolymer increases with isosorbide monomer content up to about 200° C.for the isosorbide terephthalate homopolymer. The polymer samples weremade by reacting terephthaloyl dichloride in solution with the diolmonomers. This method yielded a copolymer with a molecular weight thatis apparently higher than was obtained in the German Patent Applicationdescribed above but still relatively low when compared against otherpolyester polymers and copolymers. Further, these polymers were made bysolution polymerization and were thus free of diethylene glycol moietiesas a product of polymerization. See R. Storbeck, Dissertation,Universitat Karlsruhe (1994); R. Storbeck, et al., J. Appl. PolymerScience, Vol. 59, pp. 1199-1202 (1996).

U.S. Pat. No. 4,418,174 describes a process for the preparation ofpolyesters useful as raw materials in the production of aqueous stovinglacquers. The polyesters are prepared with an alcohol and an acid. Oneof the many preferred alcohols is dianhydrosorbitol. However, theaverage molecular weight of the polyesters is from 1,000 to 10,000, andno polyester actually containing a dianhydrosorbitol moiety was made.

U.S. Pat. No. 5,179,143 describes a process for the preparation ofcompression molded materials. Also, described therein are hydroxylcontaining polyesters. These hydroxyl containing polyesters are listedto include polyhydric alcohols, including 1,4:3,6-dianhydrosorbitol.Again, however, the highest molecular weights reported are relativelylow, i.e., 400 to 10,000, and no polyester actually containing the1,4:3,6-dianhydrosorbitol moiety was made.

Published PCT Applications WO 97/14739 and WO 96/25449 describecholesteric and nematic liquid crystalline polyesters that includeisosorbide moieties as monomer units. Such polyesters have relativelylow molecular weights and are not isotropic.

Currently, high molecular weight polyesters containing an isosorbidemoiety have not been blended with other thermoplastic polymers.

SUMMARY OF THE DISCLOSURE

Contrary to the teachings and expectations that have been published inthe prior art, isotropic, i.e., semi-crystalline and amorphous or nonliquid crystalline, copolyesters containing terephthaloyl moieties,ethylene glycol moieties, isosorbide moieties and, optionally,diethylene glycol moieties are readily synthesized in molecular weightsthat are suitable for making fabricated products, such as films,beverage bottles, molded products, sheets and fibers on an industrialscale.

The polymers used, depend on the polymer composition that is desired.The amount of each polymer is desirably chosen so that the finalpolymeric product possesses the desired property.

The polyester desirably contains terephthaloyl moieties, ethylene glycolmoieties, isosorbide moieties and, optionally, diethylene glycolmoieties arranged to provide a useful high molecular weight polymerwhich may be blended with one or more of the thermoplastic polymers.

In a preferred embodiment, the number of terephthaloyl moieties in thepolyester polymer is in the range of about 25% to about 50 mole % (mole% of the total polymer). The polyester polymer may also include amountsof one or more other aromatic diacid moieties such as, for example,those derived from isophthalic acid, 2,5-furandicarboxylic acid,2,5-thiophenedicarboxylic acid, 2,6-naphthalene-dicarboxylic acid,2,7-naphthalenedicarboxylic acid, and 4,4'-bibenzoic acid, at combinedlevels up to about 25 mole % (mole % of the total polymer).

In a preferred embodiment, ethylene glycol monomer units are present inthe polyester polymer in amounts of about 5 mole % to about 49.75 mole%. The polyester polymer may also contain diethylene glycol moieties.Depending on the method of manufacture, the amount of diethylene glycolmoieties in the polyester polymer is in the range of about 0.0 mole % toabout 25 mole %.

In a preferred embodiment, isosorbide is present in the polyesterpolymer in amounts in the range of about 0.25 mole % to about 40 mole %.One or more other diol monomer units may also be included in thepolyester polymer in amounts up to a total of about 45 mole %.

Of course, all of the percentages are dependent on the particularapplication desired. Desirably, however, equimolar amounts of diacidmonomer units and diol monomer units are present in the polyesterpolymer. This balance is desirable to achieve a high molecular weightpolyester polymer.

The polyester polymer has an inherent viscosity, which is an indicatorof molecular weight, of at least about 0.35 dL/g, as measured on a 1%(weight/volume) solution of the polymer in o-chlorophenol at atemperature of 25° C. This inherent viscosity is sufficient for someapplications, such as some optical articles and coatings. For otherapplications, such as compact discs, an inherent viscosity of about 0.4dL/g is preferred. Higher inherent viscosities, such as at least about0.5 dL/g are needed for many other applications (e.g. bottles, films,sheet, molding resin). Further processing of the polyester polymer mayachieve even higher inherent viscosities.

The polyester polymer is blended with one or more other thermoplasticpolymers. The other thermoplastic polymers suitable for use in theblends of the present invention include polycarbonates; styrene resins;alkyl acrylate resins; polyurethanes; vinyl chloride polymers;polyarylethers; copolyetherester block polymers; polyhydroxyethers;polyarylates; other polyesters or mixtures thereof.

The ratio of polyester polymer to other thermoplastic polymer may varywidely depending on the desired properties.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS OF THE DISCLOSURE

The blends of the present invention are described below in terms of thepolyesters and other thermoplastic polymers that may be included withinthe blends.

Polyester Polymers Containing Isosorbide Moieties

The polyester polymer, described in detail below, may be made by themelt condensation of a combination of monomers containing an ethyleneglycol moiety, an isosorbide moiety and a terephthaloyl moiety. Smallamounts of other monomers may be added during the polymerization or maybe produced as by-products during the reaction.

In a preferred embodiment, ethylene glycol monomer units are present inamounts of about 5 mole % to about 49.75 mole %, preferably 10 mole % toabout 49.5 mole %, more preferably about 25 mole % to about 48 mole %,and even more preferably about 25 mole % to about 40 mole %. Thepolyester polymer may also contain diethylene glycol monomer units.Depending on the method of manufacture, the amount of diethylene glycolmonomer units is in the range of about 0.0 mole % to about 25 mole %,preferably 0.25 mole % to about 10 mole %, and more preferably 0.25 mole% to about 5 mole %. Diethylene glycol may be produced as a by-productof the polymerization process, and may also be added to help accuratelyregulate the amount of diethylene glycol monomer units that are in thepolyester polymer.

In a preferred embodiment, isosorbide moieties are present in thepolyester polymer in amounts in the range of about 0.25 mole % to about40 mole %, preferably about 0.25 mole % to about 30 mole %, and morepreferably about 0.5 mole % to 20 mole %. Depending on the application,isosorbide may be present in any desirable range such as 1 mole % to 3mole %, 1 mole % to 6 mole %,1 mole % to 8 mole % and 1 mole % to 20mole %. One or more other diol monomer units may optionally be includedin amounts up to a total of about 45 mole %, preferably less than 20mole %, and even more preferably less than 15 mole %, even morepreferably less than 10 mole % and even more preferably less than 2 mole%. Examples of these optional other diol units include aliphaticalkylene glycols having from 3-12 carbon atoms and having the empiricalformula HO--C_(n) H_(2n) --OH, where n is an integer from 3-12,including branched diols such as 2,2-dimethyl-1,3-propanediol; cis ortrans-1,4-cyclohexanedimethanol and mixtures of the cis and transisomers; triethylene glycol; 2,2-bis[4-(2-hydroxyethoxy)phenyl] propane;1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane;9,9-bis[4-(2-hydroxyethoxy)-phenyl]fluorene; 1,4:3,6-dianhydromannitol;1,4:3,6-dianhydroiditol; and 1,4-anhydroerythritol.

In a preferred embodiment, the number of terephthaloyl moieties in thepolyester polymer is in the range of about 25 mole % to about 50 mole %more preferably about 40 mole % to about 50 mole %, even more preferablyabout 45 mole % to about 50 mole % (mole % of the total polymer). Thepolyester polymer may also include amounts of one or more other aromaticdiacid moieties such as, for example, those derived from isophthalicacid, 2,5-furandicarboxylic acid, 2,5-thiophenedicarboxylic acid,2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and4,4'-bibenzoic acid, at combined levels up to about 25 mole %,preferably up to 10 mole %, more preferably up to about 5 mole % (mole %of the total polymer).

Of course, all of the percentages are dependent on the particularapplication desired. Desirably, however, equimolar amounts of diacidmonomer units and diol monomer units are present in the polyesterpolymer. This balance is desirable to achieve a high molecular weight.

The polyester polymer has an inherent viscosity, which is an indicatorof molecular weight, of at least about 0.35 dL/g, as measured on a 1%(weight/volume) solution of the polymer in o-chlorophenol at atemperature of 25° C. This inherent viscosity is sufficient for someapplications, such as some optical articles and coatings. For otherapplications, such as compact discs, an inherent viscosity of about 0.4dL/g is preferred. Higher inherent viscosities are needed for many otherapplications (e.g. bottles, films, sheet, molding resin). The conditionscan be adjusted to obtain desired inherent viscosities up to at leastabout 0.5 and desirably higher than 0.65 dL/g. Further processing of thepolyester may achieve inherent viscosities of 0.7, 0.8, 0.9, 1.0, 1.5,2.0 dL/g and even higher.

The molecular weight is normally not measured directly. Instead, theinherent viscosity of the polymer in solution or the melt viscosity isused as an indicator of molecular weight. For the present polyesterpolymers, the inherent viscosity is measured by the method describedpreviously, with a molecular weight corresponding to an inherentviscosity of about 0.35 or more being sufficient for some uses. Highermolecular weights, corresponding to inherent viscosities of about 0.45or more, may be required for other applications. Generally, the inherentviscosity/ molecular weight relationship can be fitted to a linearequation:

    log(I.V.)=0.5856×log(Mw)-2.9672.

The inherent viscosities are a better indicator of molecular weight forcomparisons of samples and are used as the indicator of molecular weightherein.

The melt process conditions for making the polyester polymer,particularly the amounts of monomers used, depend on the polyesterpolymer composition that is desired. The amount of diol and diacid ordimethyl ester thereof are desirably chosen so that the final polymericproduct contains the desired amounts of the various monomer units,desirably with equimolar amounts of monomer units derived from the diolsand the diacids. Because of the volatility of some of the monomers,including isosorbide, and depending on such variables as whether thereactor is sealed (i.e. is under pressure) and the efficiency of thedistillation columns used in synthesizing the polymer, some of themonomers may need to be included in excess at the beginning of thepolymerization reaction and removed by distillation as the reactionproceeds. This is particularly true of ethylene glycol and isosorbide.

The exact amount of monomers to be charged to a particular reactor isreadily determined by a skilled practitioner, but often will be in theranges below. Excesses of ethylene glycol and isosorbide are desirablycharged, and the excess ethylene glycol and isosorbide are removed bydistillation or other means of evaporation as the polymerizationreaction proceeds. Terephthalic acid or dimethyl terephthalate isdesirably included in an amount of about 50% to about 100 mole %, morepreferably 80 mole % to about 100 mole % of the diacid monomers that arecharged, with the remainder being the optional diacid monomers.Isosorbide is desirably charged in an amount of about 0.25 mole % toabout 150 mole % or more compared with the total amount of diacidmonomers. The use of diethylene glycol monomer is optional, and is oftenmade in situ. If diethylene glycol is added, it is charged in an amountup to about 20 mole % of the total amount of diacid monomers. Ethyleneglycol is charged in an amount in the range of about 5 mole % to about300 mole %, desirably 20 mole % to about 300 mole % of the diacidmonomers, and the optional other diols are charged in an amount up toabout 100 mole % of the diacid monomers.

The ranges given for the monomers used to make up the polyester polymerare very wide because of the wide variation in monomer loss duringpolymerization, depending on the efficiency of distillation columns andother kinds of recovery and recycle systems, and are only anapproximation. Exact amounts of monomers that are charged to a specificreactor to achieve a specific composition are readily determined by askilled practitioner.

In the polyester polymerization process, the monomers are combined, andare heated gradually with mixing with a catalyst or catalyst mixture toa temperature in the range of about 260° C. to about 300° C., desirably280° C. to about 285° C. The exact conditions and the catalysts dependon whether the diacids are polymerized as true acids or as dimethylesters. The catalyst may be included initially with the reactants,and/or may be added one or more times to the mixture as it is heated.The catalyst used may be modified as the reaction proceeds. The heatingand stirring are continued for a sufficient time and to a sufficienttemperature, generally with removal by distillation of excess reactants,to yield a molten polyester polymer having a high enough molecularweight to be suitable for making fabricated products.

Catalysts that may be used include salts of Li, Ca, Mg, Mn, Zn, Pb, Sb,Sn, Ge, and Ti, such as acetate salts and oxides, including glycoladducts, and Ti alkoxides. These are generally known in the art, and thespecific catalyst or combination or sequence of catalysts used may bereadily selected by a skilled practitioner. The preferred catalyst andpreferred conditions differ depending on whether the diacid monomer ispolymerized as the free diacid or as a dimethyl ester. Germanium andantimony containing catalysts are the most preferred.

The monomer composition of the polyester polymer is chosen for specificuses and for specific sets of properties. For uses where a partiallycrystalline polymer is desired, as for example food and beveragecontainers, such as hot fill or cold fill bottles, fibers, and films,the polymer will generally have a monomer composition in the range ofabout 0.1% to about 10%, preferably about 0.25% to about 5% on a molarbasis of isosorbide moieties, about 49.9 to about 33% on a molar basisof ethylene glycol moieties, about 0.0 to 5.0%, preferably 0.25% toabout 5% on a molar basis of diethylene glycol moieties, and not morethan about 2% on a molar basis of other diol moieties, such as1,4-cyclohexanedi methanol. For the bottle resins, the diacid comprisesterephthaloyl moieties at a level of about 35% to about 50% on a molarbasis, and optional other aromatic diacid moieties at levels of up toabout 15% on a molar basis, where the optional aromatic diacid moietiesmay be derived from 2,6-naphthalenedicarboxylic acid, isophthalic acid,4,4'-bibenzoic acid, and mixtures thereof.

For applications where it is desirable to have an amorphous polymer,such as would be used to make transparent optical articles, the amountof isosorbide moiety is in the range of about 2% to about 30% on a molarbasis, the ethylene glycol moieties are present in an amount of about10% to about 48% on a molar basis, optional other diols such as1,4-cyclohexanedimethanol moieties are present in an amount up to about45% on a molar basis, diethylene glycol moieties are present in anamount of about 0.0% to about 5%, preferably 0.25% to about 5% on amolar basis, terephthaloyl moieties are present at a level of about 25%to about 50%, and other optional diacid moieties, such as2,6-naphthalenedicarboxylic acid, isophthalic acid, 4,4'-bibenzoic acid,and mixtures thereof, are present in amounts up to a total of about 25%,on a molar basis.

Some of these compositions (i.e. those having isosorbide at levels ofless than about 12%) are semi-crystalline if they are cooled slowly fromthe melt or if they are annealed above their glass transitiontemperatures, but are amorphous if they are cooled rapidly from themelt. In general, the compositions that can be semi-crystalline areslower to crystallize than poly(ethylene terephthalate) compositions, sothat it is easier to make transparent articles that remain transparentusing crystallizable copolymers even though they may be exposed toconditions under which they can crystallize.

The polyesters of the invention can be made by any of several methods.The product compositions vary somewhat depending on the method used,particularly in the amount of diethylene glycol moieties that arepresent in the polymer. These methods include the reaction of the diolmonomers with the acid chlorides of terephthalic acid and any otheracids that may be present. The reaction of terephthaloyl dichloride withisosorbide and ethylene glycol is readily carried out by combining themonomers in a solvent (e.g. toluene) in the presence of a base, such aspyridine, which neutralizes HCl as it is produced. This procedure isdescribed in R. Storbeck et al., J. Appl. Polymer Science, Vol. 59, pp.1199-1202 (1996). Other well-known variations using terephthaloyldichloride may also be used (e.g. interfacial polymerization), or themonomers may simply be stirred together while heating.

When the polymer is made using the acid chlorides, the ratio of monomerunits in the product polymer is about the same as the ratio of reactingmonomers. Therefore, the ratio of monomers charged to the reactor isabout the same as the desired ratio in the product. A stoichiometricequivalent of the diol and diacids generally will be used to obtain ahigh molecular weight polymer, e.g., one with an inherent viscosity ofat least about 0.35 dL/g, suitable for making films.

The polymers can also be made by a melt polymerization process, in whichthe acid component is either terephthalic acid or dimethyl terephthlate,and also may include the free acid or dimethyl ester of any otheraromatic diacids that may be desired in the polyester polymercomposition. The diacids or dimethyl esters are heated with the diols(ethylene glycol, isosorbide, optional diols) in the presence of acatalyst to a high enough temperature that the monomers combine to formesters and diesters, then oligomers, and finally polymers. The polymericproduct at the end of the polymerization process is a molten polymer.The diol monomers (e.g., ethylene glycol and isosorbide) are volatileand distill from the reactor as the polymerization proceeds. Therefore,an excess of these diols is desirably charged to the reaction to obtaina polymer, and the amounts must be adjusted according to thecharacteristics of the polymerization vessel, such as the efficiency ofthe distillation column and the efficiency of monomer recovery andrecycle. Such modifications in the amounts of monomers and the like inaccordance with the characteristics of a reactor are readily made bypractitioners in the art.

The above-described melt polymerization process is the preferred methodof making the polymer and is described in detail in commonly assignedU.S. Pat. No. 5,959,066, issued Sep. 28, 1999. The melt polymerizationprocesses using dimethyl terephthalate and terephthalic acid are alsosummarized below.

Dimethyl Terephthalate Process

In this process, which is carried out in two steps, terephthalic acidand the optional diacid monomers, if present, are used as their dimethylester derivatives. In minor amounts, e.g., 1-2 wt %, free diacids mayalso be added. The diols (e.g. ethylene glycol and isosorbide) are mixedwith the dimethyl ester of the aromatic diacid (e.g. dimethylterephthalate) in the presence of an ester interchange catalyst, whichcauses exchange of the ethylene glycol for the methyl group of thedimethyl esters through a transesterification reaction. This results inthe formation of methanol, which distills out of the reaction flask, andbis (2-hydroxyethylterephthalate). Because of the stoichiometry of thisreaction, somewhat more than two moles of ethylene glycol are desirablyadded as reactants for the ester interchange reaction.

Catalysts that bring about ester interchange include salts (usuallyacetates) of the following metals: Li, Ca, Mg, Mn, Zn, Pb, andcombinations thereof, Ti(OR)₄, where R is an alkyl group having 2-12carbon atoms, and PbO. The catalyst components are generally included inan amount of about 10 ppm to about 100 ppm. Preferred catalysts forester interchange include Mn(OAc)₂, Co(OAc)₂, and Zn(OAc)₂, where OAc isthe abbreviation for acetate, and combinations thereof. Thepolycondensation catalyst in the second stage of the reaction,preferably Sb(III) oxide, may be added now or at the start of thepolycondensation stage. A catalyst that has been used with particularlygood success is based on salts of Mn(II) and Co(II), and at levels ofabout 50 to about 100 ppm, each. These were used in the form of Mn(II)acetate tetrahydrate and Co(II) acetate tetrahydrate, although othersalts of the same metals may also be used.

Ester interchange is desirably brought about by heating and stirring themixture of reactants under an inert atmosphere (e.g. nitrogen) atatmospheric pressure from room temperature to a temperature high enoughto induce the ester interchange (about 150° C.). Methanol is formed as aby-product and distills out of the reactor. The reaction is graduallyheated to about 250° C. until methanol evolution stops. The end ofmethanol evolution can be recognized by a drop in the overheadtemperature of the reaction vessel.

A small amount of an additive having a boiling point of 170-240° C. maybe added to the ester interchange to aid in the heat transfer within thereaction medium and to help retain volatile components in the vesselthat may sublime into the packed column. The additive must be inert andnot react with alcohols or dimethyl terephthalate at temperatures below300° C. Preferably, the additive has a boiling point greater than 170°C., more preferably within the range of 170° C. to 2400, and is used inan amount between about 0.05 and 10 wt %, more preferably between about0.25 and 1 wt % of reaction mixture. A preferred additive istetrahydronaphthalene. Other examples include diphenyl ether,diphenylsulfone and benzophenone. Other such solvents are described inU.S. Pat. No. 4,294,956, the contents of which are hereby incorporatedby reference.

The second stage of the reaction is commenced by adding apolycondensation catalyst and a sequestering agent for thetransesterification catalyst. Polyphosphoric acid is an example of asequestering agent and is normally added in an amount of about 10 toabout 100 ppm of phosphorous per gm of dimethyl terephthalate. Anexample of a polycondensation catalyst is antimony (III) oxide, whichmay be used at a level of 100 to about 400 ppm.

The polycondensation reaction is typically carried out at a temperaturefrom about 250° C. to 285° C. During this time, ethylene glycol distillsout of the reaction due to condensation of the bis(2-hydroxyethyl)terephthalate to form polymer and by-product ethylene glycol, which iscollected as a distillate.

The polycondensation reaction described above is preferably carried outunder vacuum, which can be applied while the reactor is being heated tothe temperature of the polycondensation reaction after polyphosphoricacid and Sb(III) oxide have been added. Alternatively, vacuum can beapplied after the polycondensation reaction temperature reaches 280°C.-285° C. In either case, the reaction is accelerated by theapplication of vacuum. Heating under vacuum is continued until themolten polymer reaches the desired molecular weight, usually recognizedby an increase in the melt viscosity to a pre-determined level. This isobserved as an increase in the torque needed for the stirring motor tomaintain stirring. An inherent viscosity of up to about 0.65 dL/g orgreater can be achieved by this melt polymerization process withoutfurther efforts at raising molecular weight. For certain compositionranges, the molecular weight can be increased further by solid statepolymerization, described below.

Terephthalic Acid Process

The terephthalic acid process is similar to the dimethyl terephthalateprocess except that the initial esterification reaction that leads tobis(2-hydroxyethylterephthalate) and other low molecular weight estersis carried out at a slightly elevated pressure (autogenous pressure,about 25 to 50 psig). Instead of a two-fold excess of diols, a smallerexcess (about 10% to about 60%) of diols (ethylene glycol, isosorbideand other diols, if any) is used. The intermediate esterificationproduct is a mixture of oligomers, since not enough diol is present togenerate a diester of terephthalic acid. The catalysts are alsodifferent. No added catalyst is necessary in the esterificationreaction.

A polycondensation catalyst (e.g., Sb(III) or TI(IV) salts) is stilldesirable to achieve a high molecular weight polymer. The catalyst thatis needed to achieve a high molecular weight can be added after theesterification reaction, or it can be conveniently charged with thereactants at the beginning of the reaction. Catalysts that are usefulfor making a high molecular weight polymer directly from terephthalicacid and the diols include the acetate or other alkanoate salts ofCo(II) and Sb(III), oxides of Sb(III) and Ge(IV), and Ti(OR)₄ (where Ris an alkyl group having 2 to 12 carbon atoms). Glycol solubilizedoxides of these metal salts may also be used. The use of these and othercatalysts in the preparation of polyesters is well-known in the art.

The reaction may be carried out in discrete steps, but this is notnecessary. In practice on a large scale, it may be carried out in stepsas the reactants and intermediate products are pumped from reactor toreactor at increasing temperatures. In a batch process, the reactantsand catalyst may be charged to a reactor at room temperature and thengradually heated to about 285° C. as polymer forms. The pressure isvented in the range of about 200° C. to about 250° C., and a vacuum isthen desirably applied.

Esterification to form bis(2-hydroxyethylterephthalate) esters andoligomers takes place at elevated temperatures (between room temperatureand about 220° C. to 265° C. under autogenous pressure), and polymer ismade at temperatures in the range of about 275° C. to about 285° C.under a high vacuum (less than 10 Torr, preferably less than 1 Torr).The vacuum is needed to remove residual ethylene glycol, isosorbide andwater vapor from the reaction to raise the molecular weight.

A polymer having an inherent viscosity of at least 0.5 dL/g, andgenerally up to about 0.65 dL/g can be achieved by the directpolymerization process, without subsequent solid state polymerization.The progress of the polymerization can be followed by the meltviscosity, which is easily observed by the torque that is required tomaintain stirring of the molten polymer.

Solid State Polymerization

Polymers can be made by the melt condensation process described abovehaving an inherent viscosity of at least about 0.5 dL/g, and often ashigh as about 0.65 dL/g, or greater without further treatment, measuredby the method described above. This corresponds to a molecular weightthat is suitable for many applications (e.g. molded products). Polymerswith lower inherent viscosities can also be made, if desired, as forcompact discs. Other applications, such as bottles, may require a stillhigher molecular weight. Compositions of ethylene glycol, isosorbide,and terephthalic acid having isosorbide in an amount of about 0.25% toabout 10% on a mole basis may have their molecular weight increasedfurther by solid state polymerization. The product made by meltpolymerization, after extruding, cooling, and pelletizing, isessentially non-crystalline. The material can be made semi-crystallineby heating it to a temperature in the range of about 11 5° C. to about140° C. for an extended period of time (about 2 to about 12 hours). Thisinduces crystallization so that the product can then be heated to a muchhigher temperature to raise the molecular weight. The process works bestfor low levels of isosorbide (about 0.25 mole % to about 3 mole %),because the polyester crystallizes more easily with low levels ofisosorbide.

The polymer may also be crystallized prior to solid state polymerizationby treatment with a relatively poor solvent for polyesters such asacetone which induces crystallization. Such solvents reduce glasstransition temperature (Tg) allowing for crystallization. Solventinduced crystallization is known for polyesters and is described in U.S.Pat. Nos. 5,164,478 and 3,684,766, which are incorporated herein byreference.

The crystallized polymer is subjected to solid state polymerization byplacing the pelletized or pulverized polymer into a stream of an inertgas, usually nitrogen, or under a vacuum of 1 Torr, at an elevatedtemperature, above about 140° C. but below the melting temperature ofthe polymer for a period of about two to 16 hours. Solid statepolymerization is generally carried out at a temperature in the range ofabout 1900 to about 210° C. for a period of about two to about 16 hours.Good results are obtained by heating the polymer to about 195° to about198° C. for about 10 hours. This solid state polymerization may raisethe inherent viscosity to about 0.8 dL/g or higher.

Thermoplastic Polymers

The thermoplastic polymers suitable for use in this invention arepolycarbonates, styrene resins, alkyl acrylate resins, polyurethanes,vinyl chloride polymers, polyarylethers, copolyetherester blockpolymers, polyhydroxyethers, polyarylates, and other polyesters ormixtures thereof.

The thermoplastic polymers for use in the present application furtherinclude those polymers known to those skilled in the art for blendingwith, e.g., polyethylene terephthalate and polybutylene terephthalatebased polyesters such as described on page 42 of Encyclopedia ofCommercial Polymer Blends, ChemTech Publishing, Toronto (1994), thecontents of which are hereby incorporated by reference, and as describedin Appendices I.B, I.C and I.D and each of the patents described inAppendices II.B, II.E and II.F of Polymer Alloys and BlendsThermodynamics and Rheology, Hanser Publishers, distributed in theUnited States by Oxford University Press, NY (1990), the contents ofeach Appendix and the listed patents hereby being incorporated byreference including specifically the compositional listings ofAppendices II.B, II.E and II.F.

Also specifically contemplated are the thermoplastic polymers which aredescribed in U.S. Pat. No. 4,259,458, the contents of which are herebyincorporated by reference. These thermoplastic polymers are morespecifically described below.

A. Polycarbonate

The thermoplastic aromatic polycarbonates that can be employed hereinare homopolymers and copolymers and mixtures thereof which have anintrinsic viscosity of 0.35 to 2.0 dL/g as measured above. Typical ofsome of the dihydric phenols that may be employed in the practice ofthis invention are bisphenol-A (2,2-bis(4-hydroxyphenyl)propane),bis(4-hydroxphenyl)methane,2,2-bis(4-hydroxy-3-methylphenyl) propane,4,4-bis(4-hydroxyphenyl) heptane, 4,4'-(3,3,5-trimethylcyclohexylidene)diphenol, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl) propane,2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)-propane,(3,3'-dichloro-4,4'-dihydroxydiphenyl) methane. Other dihydric phenolsof the bisphenol-type are also available and are disclosed in U.S. Pat.Nos. 2,999,835, 3,028,365 and 3,334,154.

It is, of course, possible to employ two or more different dihydricphenols or a copolymer of a dihydric phenol with a glycol or withhydroxy or acid terminated polyester, or with a dibasic acid in theevent a carbonate copolymer or inter-polymer rather than a homopolymeris desired for use in the preparation of the aromatic carbonate polymersof this invention.

The carbonate precursor may be either a carbonyl halide, a carbonateester or a haloformate. The carbonyl halides which can be employedherein are carbonyl bromide, carbonyl chloride and mixtures thereof.Typical of the carbonate esters which may be employed herein arediphenyl carbonate, di-(halophenyl) carbonates such asdi-(chlorophenyl)carbonate, di-(bromophenyl) carbonate,di-(trichlorophenyl) carbonate, di-(tribromophenyl) carbonate, etc.,di-(alkylphenyl) carbonates such as di(tolyl)carbonate, etc.,di-(naphthyl) carbonate, di-(chloronaphthyl) carbonate, phenyl tolylcarbonate, chlorophenyl chloronaphthyl carbonate, etc., or mixturesthereof. The haloformates suitable for use herein includebis-haloformates of dihydric phenols (for example, bischloroformates ofbisphenol-A, of hydroquinone, etc.) or glycols (for example,bishaloformates of ethylene glycol, neopentyl glycol, polyethyleneglycol, etc.). While other carbonate precursors will occur to thoseskilled in the art, carbonyl chloride, also known as phosgene, ispreferred.

The aromatic carbonate polymers of this invention may be prepared byusing phosgene or a haloformate and by employing a molecular weightregulator, an acid acceptor and a catalyst. The molecular weightregulators which can be employed in carrying out the process of thisinvention include monohydric phenols such as phenol,para-tertiarybutylphenol, para-bromophenol, primary and secondaryamines, i etc. Preferably, a phenol is employed as the molecular weightregulator.

A suitable acid acceptor may be either an organic or an inorganic acidacceptor. A suitable organic acid acceptor is a tertiary amine andincludes such materials as pyridine, triethylamine, dimethylaniline,tributylamine, etc. The inorganic acid acceptor may be one which can beeither a hydroxide, a carbonate, a bicarbonate, or a phosphate of analkali or alkaline earth metal.

The catalysts which are employed herein can be any of the suitablecatalysts that aid the polymerization of bisphenol-A with phosgene.Suitable catalysts include tertiary amines such as, for example,triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammoniumcompounds such as, for example, tetraethylammonium bromide, cetyltriethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethyl ammoniumhydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammoniumchloride and quaternary phosphonium compounds such as, for example,n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphoniumbromide.

The polycarbonates can be prepared in a one-phase (homogeneous solution)or two-phase (interfacial) systems, when phosgene or a haloformate areused. Bulk reactions are possible with the diarylcarbonate precursors.

B. Styrene Resin

Styrene resins suitable for use herein include ABS-type polymers, themolecules of which consist of two or more polymeric parts of differentcompositions that are bonded chemically. The polymer is preferablyprepared by polymerizing a conjugated diene such as butadiene or aconjugated diene with a monomer copolymerizable therewith such asstyrene to provide a polymeric backbone. After formation of thebackbone, at least one grafting monomer and preferably two arepolymerized in the presence of the prepolymerized backbone to obtain thegraft polymer.

The backbone polymer, as mentioned, is preferably a conjugated dienepolymer such as polybutadiene polyisoprene, or a copolymer such asbutadiene-styrene, butadiene-acrylonitrile, or the like.

The specific conjugated diene monomers normally utilized in preparingthe backbone of the graft polymer portion of the blends of thisinvention are generically described by the formula: ##STR2## wherein Xmay be selected from the group consisting of hydrogen, alkyl groupscontaining from one to five carbon atoms, chloro and bromo. Examples ofdienes that may be used are butadiene, isoprene; 1,3-heptadiene;methyl-1,3-pentadiene; 2,3-dimethyl-1,3-butadiene; 1,3-pentadiene;2-methyl-3-ethyl-1,3-butadiene; 2-ethyl-1,3-pentadiene; 1,3-and2,4-hexadienes, chloro and bromo substituted butadienes such asdichlorobutadiene, bromobutadiene, dibromobutadiene, mixtures thereof,and the like. The preferred conjugated diene utilized herein isbutadiene.

A group of monomers that may be polymerized in the presence of theprepolymerized backbone are preferably monovinylaromatic hydrocarbons.The monovinyl-aromatic monomers utilized are generically described bythe formula: ##STR3## wherein X may be selected from the groupconsisting of hydrogen, alkyl groups containing from one to five carbonatoms, chloro and bromo. Examples of the monovinylaromatic compounds andsubstituted monovinylaromatic compounds that may be used are styrene andother vinyl substituted aromatic compounds including alkyl-,cycloalkyl-, aryl-, alkaryl-, aralkyl-, alkoxy-, aryloxy-, and othersubstituted vinylaromatic compounds. Examples of such compounds are3-methylstyrene; 3,5-diethylstyrene and 4-n-propylstyrene,α-methylstyrene, α-methyl vinyltoluene, α-chlorostyrene,α-bromo-styrene, dichlorostyrene, dibromostyrene, tetra-chlorostyrene,mixtures thereof, and the like. The preferred monovinylaromatichydrocarbons used therein are styrene and/or α-methylstyrene.

A second group of monomers that may be polymerized in the presence ofthe prepolymerized backbone are acrylonitrile, substituted acrylonitrileand/or acrylic acid esters exemplified by acrylonitrile and alkylacrylates such as methyl methacrylate. The acrylonitrile, substitutedacrylonitrile, or acrylic acid esters are described generically by theformula: ##STR4## wherein X may be selected from the group consisting ofhydrogen, alkyl groups containing from one to five carbon atoms, chloroand bromo and Y is selected from the group consisting of cyano andcarbalkoxy wherein the alkyl group of the carbalkoxy group contains fromone to about twelve carbon atoms. Examples of monomers of thisdescription are acrylonitrile, ethacrylonitrile, methacrylonitrile,α-chloroacrylonitrile, β-chloroacrylonitrile, α-bromoacrylonitrile, andβ-bromoacrylonitrile, methyl acrylate, methyl methacrylate, ethylacrylate, butyl acrylate, propyl acrylate, isopropyl acrylate, isobutylacrylate, mixtures thereof and the like. The preferred acrylic monomerused herein is acrylonitrile and the preferred acrylic acid esters areethyl acrylate and methyl methacrylate.

In the preparation of the graft polymer, the conjugated diolefin polymeror copolymer exemplified by 1,3-butadiene polymer or copolymer comprisesfrom about 50% by weight to about 5% by weight of the total graftpolymer composition and the monomers polymerized in the presence of thebackbone exemplified by styrene and acrylonitrile comprise from about 40to about 95% by weight of the total graft polymer composition.

The second group of grafting monomers, exemplified by acrylonitrile,ethyl acrylate or methyl methacrylate, of the graft polymer composition,preferably comprise from about 10% to about 40% by weight of the totalgraft copolymer composition and the monovinylaromatic hydrocarbonexemplified by styrene comprise from about 30 to about 70% by weight ofthe total graft polymer composition.

In preparing the polymer, it is normal to have a certain percentage ofthe polymerizing monomers that are grafted on the backbone combine witheach other and occur as free copolymer. If styrene is utilized as one ofthe grafting monomers and acrylonitrile as the second grafting monomer,a certain portion of the composition will copolymerize as freestyrene-acrylonitrile copolymer. In the case where α-methylstyrene (orother monomer) is substituted for the styrene in the compositions usedin preparing the graft polymer, a certain percentage of the compositionmay be an α-methylstyrene-acrylonitrile copolymer. Also, there areoccasions where a copolymer, such as α-methylstyrene-acrylonitrile, isadded to the graft polymer copolymer blend. When the graftpolymer-copolymer blend is referred to herein, it is meant optionally toinclude at least one copolymer blended with the graft polymer. It iscontemplated in this invention that the graft polymer composition maycontain up to 90% of free copolymer.

Optionally, the elastomeric backbone may be an acrylate rubber such asone based on n-butyl acrylate, ethylacrylate, 2-ethylhexylacrylate, andthe like. Additionally, minor amounts of a diene may be copolymerized inthe acrylate rubber backbone to yield improved grafting with the matrixpolymer.

While not previously mentioned, styrene maleic anhydride-type polymersmay be used in the blends of the present invention.

C. Alkyl Acrylate Resin

The alkyl acrylate resin used in the present invention includes ahomopolymer of methyl methacrylate (i.e. polymethyl methacrylate) or acopolymer of methyl methacrylate with a vinyl monomer (e.g.acrylonitrile, N-allylmaleimide, N-vinyl maleimide, or an alkyl acrylateor methacrylate in which the alkyl group contains from 1 to 8 carbonatoms such as methyl acrylate, ethyl acrylate, butyl acrylate, ethylmethacrylate and butyl methacrylate). The amount of methyl methacrylateis not less than 70% by weight of this copolymer resin. The methylmethacrylate resin may have a reduced viscosity of from 0.1 to 2.0 dL/gin a 1% chloroform solution at 25° C.

The alkyl acrylate resin may be grafted onto an unsaturated elastomericbackbone such as polybutadiene, polyisoprene, and/or butadiene orisoprene copolymers. In the case of the graft copolymer, the alkylacrylate resin comprises greater than 50 weight percent of the graftcopolymers.

D. Polyurethanes

These thermoplastic polyurethanes may be synthesized by methodsdisclosed in U.S. Pat. No. 3,214,411 incorporated herein by reference. Aparticularly useful polyester resin used as a starting material for thethermoplastic polyurethane are those produced from adipic acid and aglycol having at least one primary hydroxyl group. The adipic acid iscondensed with a suitable glycol or mixture of glycols which have atleast one primary hydroxyl group. The condensation is stopped when anacid number of from about 0.5 to about 2.0 is reached. The water formedduring the reaction is removed simultaneously therewith or subsequentlythereto such that the final water contents is from about 0.01 to about0.2%, preferably from about 0.01 to 0.05%.

Any suitable glycol may be used in reaction with the adipic acid suchas, for example, ethylene glycol, propylene glycol, butylene glycol,hexanediol, bis-(hydroxymethylcyclohexane), 1,4-butanediol, diethyleneglycol, 2,2-dimethyl propylene glycol, 1,3-proplylene glycol and thelike. In addition to the glycols, a small amount of trihydric alcohol ofup to about 1% may be used along with the glycols such as, for example,trimethylolpropane, glycerol, hexanetriol and the like. The resultinghydroxyl polyester has a molecular weight of at least about 600, ahydroxyl number of about 25 to about 190 and preferably between about 40and about 60, and acid number of between about 0.5 and about 2 and awater content of 0.01 to about 0.2%.

The organic diisocyanate to be used in the preparation of the elastomeris preferably 4,4'-diphenylmethane diisocyanate. It is desired that the4,4'-diphenylmethane diisocyanate contain less than 5% of2,4'-diphenylmethane diisocyanate and less than 2% of the dimer ofdiphenylmethane diisocyanate. It is further desired that the aciditycalculated as HCl is from about 0.0001 to about 0.02%. The aciditycalculated as percent HCl is determined by extracting the chloride fromthe isocyanate in a hot aqueous methanol solution or by liberating thechloride on hydrolysis with water and titrating the extract with astandard silver nitrate solution to obtain the chloride ionconcentration present.

Other diisocyanates may be used in preparing the thermoplasticprocessable polyurethanes such as ethylene diisocyanate, ethylidenediisocyanate, propylene diisocyanate, butylene diisocyanate,cyclopentylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate,cyclohexylene-1,2-diisocyanate, 2,4-toluylene diisocyanate,2,6-toluylene diisocyanate, 2,2-diphenylpropane-4,4'-diisocyanate,p-phenylene diisocyanate, m-phenylene diisocyanate, xylylenediisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylenediisocyanate, diphenyl-4,4'-diisocyanate, azobenzene-4,4'-diisocyanate,diphenyl sulfone-4,4'-diisocyanate, dichlorohexamethylene diisocyanate,pentamethylene diisocyanate, hexamethylene diisocyanate,1-chlorobenzene-2,4-diisocyanate, furfurylidene diisocyanate and thelike.

Any suitable chain extending agent having active hydrogen containinggroups reactive with isocyanate groups may be used such as, for example,diols including ethylene glycol, propylene glycol, 1,4-butanediol,butenediol, butynediol, xylylene glycols, amylene glycols,1,4-phenylene-bis-β-hydroxy ethyl ether, 1,3-phenylene-bis-β-hydroxyethyl ether, bis-(hydroxy-methylcyclohexane), hexanediol, thiodiglycoland the like; diamines including ethylene diamine, propylene diamine,butylene diamine, hexamethylene diamine, cyclohexylene diamine,phenylene diamine, toluylene diamine, xylylene diamine,3,3'-dichlorobenzidine, 3,3'-dinitrobenzidine and the like; alkanolamines such as, for example, ethanol amine, aminopropyl alcohol,2,2-dimethyl propanol amine, 3-aminocyclohexyl alcohol, p-aminobenzylalcohol and the like. The difunctional chain extenders mentioned in U.S.Pat. Nos. 2,620,516, 2,621,166 and 2,729,618 incorporated herein byreference may be used. If desirable, a small amount of polyfunctionalmaterial may be utilized. This polyfunctional chain extender, however,should not be present in an amount greater than about 1% by weight. Anysuitable polyfunctional compound may be used in this application suchas, for example, glycerol, trimethylolpropane, hexanetriol,pentaerythritol and the like.

In accordance with the process of this invention, the polyester, theorganic diisocyanate and the chain extender may be individually heatedpreferably to a temperature of from about 600 to about 135° C. and thenthe polyester and chain extender are substantially simultaneously mixedwith the diisocyanate. Of course, to increase the rate of reaction, anysuitable catalyst may be added to the reaction mixture such as tertiaryamines and the like as set forth in U.S. Pat. Nos. 2,620,516, 2,621,166and 2,729,618. Although adipate polyesters are preferred, polyesters maybe used which are based on succinic acid, suberic acid, sebacic acid,oxalic acid, methyl adipic acid, glutaric acid, pimelic acid, azelaicacid, phthalic acid, terephthalic acid, isophthalic acid and the like.Polyesters based on ε-caprolactone are also preferred.

A polyether may be used instead of the polyester in the preparation ofthe thermoplastic polyurethane and preferably polytetramethylene glycolhaving an average molecular weight between about 600 and 2000 andpreferably about 1000. Other polyethers such as polypropylene glycol,polyethylene glycol and the like may be used providing their molecularweight is above about 600. The above and other thermoplasticpolyurethanes such as disclosed in U.S. Pat. Nos. 2,621,166, 2,729,618,3,214,411, 2778,810, 3,012,992, Canadian Patent Nos. 754,233, 733,577and 842,325 all incorporated herein by reference may be used to producethe thermoplastic polyurethanes.

E. Vinyl Chloride Polymers

Vinyl chloride polymers for the purpose of this invention are polyvinylchloride and copolymers of vinyl chloride with olefinically unsaturatedpolymerizable compounds which contain at least 80 percent by weight ofvinyl chloride incorporated therein. Olefinically unsaturated compoundswhich are suitable for copolymerization are, for example, vinylidenehalides such as vinylidene chloride and vinylidene fluoride, vinylesters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinylchloroacetate, vinyl benzoate, acrylic and α-alkyl-acrylic acids andtheir alkyl esters, amides and nitriles, methacrylic acid, methylmethacrylate, ethyl acrylate, 2-ethyl-hexylacrylate, butyl methacrylate,acrylamide, N-methyl acrylamide, acrylonitrile and methacrylonitrile,aromatic vinyl compounds such as styrene and vinyl naphthalene andolefinically unsaturated hydrocarbons such as ethylene,bicyclo-[2,2,1]-hept-2-ene and bicyclo-[2,2,1]-hepta-2,5-dienes. Thesevinyl chloride polymers are known and can be prepared by the usualmethods of emulsion, suspension, bulk or mass polymerization. Vinylchloride polymers which have molecular weights of 40,000 to 60,000 arepreferred.

F. Poly(aryl ether)s

The poly(aryl ether) resin useful in the blend may be described as alinear, thermoplastic polyarylene polyether polysulfone, wherein thearylene units are interspersed with ether and sulfone linkages. Theseresins may be obtained by reaction of an alkali metal double salt of adihydric phenol and a dihalobenzenoid compound, either or both of whichcontain a sulfone linkage --SO₂ -- between arylene groupings, to providesulfone units in the polymer chain in addition to arylene units andether units. The polysulfone polymer has a basic structure composed ofrecurring units of the formula

    O--E--O--E'--

wherein E is the residuum of the dihydric phenol and E' is the residuumof the benzenoid compound having an inert electron withdrawing group inat least one of the positions ortho and para to the valence bonds; bothof said residua are valently bonded to the ether oxygens througharomatic carbon atoms. Such polysulfones are included within the classof polyarylene polyether resins described in U.S. Pat. No. 3,264,536,the disclosure of which is hereby incorporated herein by reference, forthe purpose of describing and exemplifying E and E' in more detail,including the preferred forms of E derived from dinuclear phenols havingthe structure: ##STR5## Ar is an aromatic group and preferably is aphenylene group. A and A₁ can be the same or different inert substituentgroups as alkyl groups having from 1 to 4 carbon atoms, halogen atoms,i.e., fluorine, chloride, bromine or iodine, or alkoxy radicals havingfrom 1 to 4 carbon atoms, r and r₁ are integers having a value of from 0to 4, inclusive, and R₁ is representative of a bond between aromaticcarbon atoms as in dihydroxydiphenyl, or is a divalent radical,including, for example, CO, O, S, S--S, SO₂ and divalent organichydrocarbon radicals such as alkylene, alkylidene, cycloalkylene, or thehalogen, alkyl, aryl or like substituted alkylene, alkylidene andcycloalkylene radicals as well as alkarylene and aromatic radicals and aring fused to both Ar groups. Typical preferred polymers are composed ofrecurring units having the formula: ##STR6## In the foregoing, formula Aand Al can be the same or different inert substituent groups as alkylgroups having from 1 to 4 carbon atoms, halogen atoms (e.g., fluorine,chlorine, bromine or iodine) or alkoxy radicals having from 1 to 4carbon atoms, r and r₁ are integers having a value of from 0 to 4,inclusive. Typically, R₁ is representative of a bond between aromaticcarbon atoms or a divalent connecting radical and R₂ represents sulfone,carbonyl, sulfoxide. Preferably, R₁ represents a bond between aromaticcarbon atoms. Even more preferred are the thermoplastic polyarylenepolysulfones of the above formula wherein r and r₁ are zero. R₁ is adivalent connecting radical of the formula ##STR7## wherein R"represents a member of the group consisting of alkyl, lower aryl, andthe halogen substituted groups thereof, and R₂ is a sulfone group.

Typical examples are the reaction products prepared from2,2-bis-(4-hydroxyphenyl) propane (source of E residue) with4,4'-dichloro-diphenylsulfone (source of E' residue) and equivalentreaction products such as those from 4,4'-dichlorodiphenylsulfone withbisphenol of benzophenone (4,4'-dihydroxydiphenyl ketone), or thebisphenol of acetophenone [1,1-bis(4-hydroxyphenyl)ethane], or thebisphenol of vinyl cyclohexane[1-ethyl-1-(4-hydroxyphenyl)-3-(4-hydroxyphenylcyclo-hexane)], or4,4'-dihydroxydiphenyl sulfone or alpha,alpha'-bis(4-hydroxyphenyl)-p-diisopropylbenzene.

Further useful discussion of the polysulfone resins which may be used isto be found in British Pat. No. 1,060,546.

G. Copolyetherester Block Copolymer

The polyetheresters consist essentially of a multiplicity of recurringintralinear long chain and short chain ester units connectedhead-to-tail through ester linkages, said long chain ester units beingrepresented by the following structure: ##STR8## and said short chainester units being represented by the following structure: ##STR9##wherein: G is a divalent radical remaining after removal of terminalhydroxy groups from a poly(alkylene oxide) glycol having a molecularweight of about 400-3500; D is a divalent radical remaining afterremoval of hydroxyl groups from a low molecular weight diol having amolecular weight less than about 250; and R₂ is a divalent radicalremaining after removal of carboxyl groups from a dicarboxylic acidhaving a molecular weight less than about 300; with the provisos thatthe short chain ester units constitute about 25-65% by weight of thecopolyester, at least about 70% of the R₂ groups must be 1,4-phenyleneradicals, at least about 70% of the D groups must be the 1,4-butyleneradicals, and the sum of the percentages of the R₂ groups which are not1,4-phenylene radicals and of the D groups which are not 1,4-butyleneradicals cannot exceed about 30%.

The term "long chain ester units" as applied to units in a polymer chainrefers to the reaction product of a long chain glycol with adicarboxylic acid. The long chain glycols of the instant invention arepoly(alkylene oxide) glycols having a molecular weight between about 400and 3500, preferably between about 600 and 2000. Copolyesters preparedfrom poly(alkylene oxide) glycols having a molecular weight of about600-2000 are preferred because they exhibit useful properties over awide range of temperature, combined with limited water swell.Copolyesters prepared from poly(alkylene oxide) glycols having amolecular weight in excess of about 3500 may crystallize and lose theirelastomeric character and good low temperature properties. Copolyesterprepared from glycols having molecular weights below about 400 haveuseful properties only within a narrow temperature range and are lesssuited for injection molding and extrusion because of a slower rate ofcrystallization of the resultant block copolymer. The long chain glycolscontain a major proportion of tetramethylene oxide units. In a preferredembodiment of the instant invention the long chain glycols will beentirely poly(tetramethylene oxide) glycol. In some instances it may bedesirable to use random or block copolymers of tetramethylene oxidecontaining minor proportions of a second alkylene oxide. Typically, thesecond monomer will constitute less than about 40 mole percent of thepoly(alkylene oxide) glycols and preferably less than 20 mole percent.Representative examples of the second monomer include 1,2- and1,3-propylene oxides, 1,2-butylene oxide and ethylene oxide.

The term "short chain ester units" as applied to units in a polymerchain refers to low molecular weight compounds or polymer chain unitshaving molecular weights less than about 550. They are made by reactinga low molecular weight diol (below about 250) with a dicarboxylic acid.

Included among the low molecular weight diols (other than1,4-butanediol) which react to form short chain ester units are acyclic,alicyclic and aromatic dihydroxy compounds. Preferred are diols with2-15 carbon atoms such as ethylene, propylene, isobutylene,tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethyleneand decamethylene glycols, dihydroxy cyclohexane, cyclohexanedimethanol, resorcinol, hydroquinone, 1,5-dihydroxy naphthalene, etc.Especially preferred are aliphatic diols containing 2-8 carbon atoms.Included among the bisphenols which can be used arebis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, andbis(p-hydroxyphenyl)propane. Equivalent esterforming derivatives ofdiols are also useful (e.g., ethylene oxide or ethylene carbonate can beused in place of ethylene glycol). The term "low molecular weight diols"as used herein should be construed to include such equivalentester-forming derivatives: provided, however, that the molecular weightrequirement pertains to the diol only and not to its derivatives.

Dicarboxylic acids (other than terephthalic acid) which are reacted withthe foregoing long chain glycols or low molecular weight diols toproduce the copolyesters of this invention are aliphatic, cycloaliphaticor aromatic dicarboxylic acids of a low molecular weight. The term"dicarboxylic acids" as used herein, includes acid equivalents of lodicarboxylic acids having two functional carboxyl groups which performsubstantially like dicarboxylic acids in reaction with glycols and diolsin forming copolyester polymers. These equivalents include esters andester-forming derivatives, such as acid halides and anhydrides. Themolecular weight requirement pertains to the acid and not to itsequivalent ester or ester-forming derivative. Thus, an ester of adicarboxylic acid having a molecular weight greater than 300 or an acidequivalent of a dicarboxylic acid having a molecular weight greater than300 are included provided the acid has a molecular weight below about300. The dicarboxylic acids can contain any substituent groups orcombinations which do not substantially interfere with the copolyesterpolymer formation and use of the polymer in the elastomeric compositionsof this invention.

Aliphatic dicarboxylic acids, as the term is used herein, refers tocarboxylic acids having two carboxyl groups each attached to a saturatedcarbon atom. If the carbon atom to which the carboxyl group is attachedis saturated and is in a ring, the acid is cycloaliphatic. Aliphatic orcycloaliphatic acids having conjugated unsaturation often can not beused because of homopolymerization. However, some unsaturated acids,such as maleic acid, can be used.

Aromatic dicarboxylic acids, as the term is used herein, aredicarboxylic acids having two carboxyl groups attached to a carbon atomin an isolated or fused benzene ring. It is not necessary that bothfunctional carboxyl groups be attached to the same aromatic ring andwhere more than one ring is present, they can be joined by aliphatic oraromatic divalent radicals such as --O-- or --SO₂ --, alkylene,alkylidene, etc.

Representative aliphatic and cycloaliphatic acids which can be used forthis invention are sebacic acid, 1,3-cyclohexane dicarboxylic acid,1,4-cyclohexane dicarboxylic acid, adipic acid, glutaric acid, succinicacid, carbonic acid, oxalic acid, azelaic acid, diethylmalonic acid,allylmalonic acid, 4-cyclohexane-1,2-dicarboxylic acid, 2-ethylsubericacid, 2,2,3,3-tetramethylsuccinic acid, cyclopentanedicarboxylic acid,decahydro-1,5-naphthylene dicarboxylic acid, 4,4-bicyclohexyldicarboxylic acid, decahydro-2,6-naphthylene dicarboxylic acid,4,4-methylenebis-(cyclohexyl) carboxylic acid, 3,4-furan dicarboxylicacid, and 1,1-cyclobutane dicarboxylic acid. Preferred aliphatic acidsare cyclohexane-dicarboxylic acids and adipic acid.

Representative aromatic dicarboxylic acids which can be used includephthalic, terephthalic and isophthalic acids, substituted dicarboxycompounds with two benzene nuclei such as bis(p-carboxyphenyl)-methane,p-carboxyphenyl/oxybenzoic acid, ethylenebis(p-oxybenzoic acid)1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,2,7-naphthalene dicarboxylic acid, phenanthrene dicarboxylic acid,anthracene dicarboxylic acid, 4,4'-sulfonyl dibenzoic acid and C₁ -C₁₂alkyl and ring substituted derivatives thereof, such as halo, alkoxy,and aryl derivatives. Hydroxy acids such as p(P-hydroxyethoxy) benzoicacid can also be used providing an aromatic dicarboxylic acid is alsopresent.

Aromatic dicarboxylic acids are a preferred class for preparing thecopolyester polymers useful for compositions of this invention. Amongthe aromatic acids, those with 8-16 carbon atoms are preferred,particularly the phenylene dicarboxylic acids, i.e., terephthalic andisophthalic acids. The most preferred copolyesters of this invention arethose prepared from dimethylterephthalate, 1,4-butanediol andpoly(tetramethylene oxide) glycol having a molecular weight from about600-1500.

Desirable polyetheresters are described in, for example, U.S. Pat. Nos.3,784,520 and 3,766,146.

H. Polyhydroxyether

The thermoplastic polyhydroxyethers in the present invention have thegeneral formula ##STR10## wherein D is the radical residuum of adihydric phenol, E" is a radical residuum of an epoxide selected frommono- and diepoxides and contains from 1 to 2 hydroxyl groups and n isan integer which represents the degree of polymerization and is at least30 and preferably is above about 80.

In general, thermoplastic polyhydroxyethers are prepared by contactingunder polymerization conditions a dihydric phenol and an epoxidecontaining from 1 to 2 epoxide groups in substantially equimolaramounts.

The product produced by the reaction between bis-phenol-A andepichiorohydrin has the repeating unit ##STR11## and can be termed apoly(monohydroxyether) of bis-phenol-A.

The product produced by the reaction between hydroquinone and butadienedioxide has the repeating unit ##STR12## and can be termed apoly(dihydroxyether) of hydroquinone.

By the use of both a monoepoxide and a diepoxidepoly(hydroxy-dihydroxyethers) can be obtained, the relative amounts ofmono- and diepoxide determining the final concentration of the mono- anddihydroxy containing repeating units E" in the polymer.

Any dihydric phenol can be used in forming polyhydroxyethers.Illustrative dihydric phenols are mononuclear dihydric phenols such ashydroquinone, resorcinol, and the like as well as the polynuclearphenols which are preferred. The dihydric polynuclear phenols have thegeneral ##STR13## formula: wherein: Ar is an aromatic divalenthydrocarbon radical such as naphthylene and phenylene with phenylenebeing preferred for the thermoplastic polyhydroxyethers used in thisinvention; B and B₁ which can be the same or different are alkylradicals such as methyl, n-propyl, n-butyl, n-hexyl, n-octyl and thelike, preferably alkyl radicals having a maximum of 4 carbon atoms; orhalogen atoms, i.e., chlorine, bromine, iodine, or fluorine; or alkoxyradicals such as methoxy, methoxymethyl, ethoxy, ethoxyethyl,n-butyloxy, amyloxy and the like, preferably an alkoxy radical having amaximum of 4 carbon atoms, a and a, are independently integers of 0 to4, R' is alkylene, alkylidene, cycloalkylene or a saturated divalentgroup. Particularly preferred are dihydric polynuclear phenols havingthe general formula: ##STR14## wherein B, B₁, a and a, are as previouslydefined, and R₃ is an alkylene or alkylidene group, preferably havingfrom 1 to 3 carbon atoms inclusive or cycloalkylene or R₃ is a saturateddivalent group such as is obtained from compounds such asvinylcyclohexane and dipentene or its isomers by reaction with two molesof phenol per mole of the compound. R₃ preferably contains from 1 to 9carbon atoms.

Diepoxides useful for the preparation of polyhydroxyethers can berepresented by the formula ##STR15## wherein R₄ is representative of abond between adjacent carbon atoms or a divalent inorganic or organicradical such as an aliphatic, aromatic, homocyclic, heterocyclic oracyclic arrangement of atoms.

By the term "diepoxide" is meant a compound containing two epoxidegroups i.e. groups containing an oxirane oxygen atom bonded to twovicinal aliphatic carbon atoms. Saturated diepoxides in which both theoxirane oxygen atoms are bonded to carbon atoms of a saturated aliphatichydrocarbon chain are particularly preferred. The term "saturateddiepoxides" refers to diepoxides which are free of ethylenicunsaturation, i.e. --C═C-- and acetylenic unsaturation, i.e.--C.tbd.C--. Diepoxides which contain solely carbon, hydrogen and oxygenatoms are especially preferred. The oxygen atoms can be (in addition tooxirane oxygen), ether oxygen, i.e. --O-- oxacarbonyl oxygen, i.e.##STR16## carbonyl oxygen, i.e. ##STR17## and the like. A singlediepoxide or a mixture of at least two diepoxides can be employed inpreparing the polydihydroxyethers of the present invention and the term"diepoxide" is intended to include a mixture of at least two diepoxides.

Other diepoxides which can be mentioned include those wherein the twooxirane groups are linked through an aromatic ether, i.e. compoundshaving the grouping ##STR18## wherein R₄ is a divalent organic radical,W is a divalent aromatic radical residuum of a dihydric phenol such asthose listed above in the description of dihydric phenols, and d is aninteger from 0 to 1 inclusive.

Still other diepoxides include ethers wherein the oxirane groups areconnected to vicinal carbon atoms at least one pair of which is a partof a cycloaliphatic hydrocarbon.

These polyhydroxy ethers are prepared by methods well known in the artsuch as those detailed in, for example, U.S. Pat. Nos. 3,238,087;3,305,528; 3,294,747 and 3,277,051.

I. Polyarylates

The polyarylates of this invention are desirably derived from a dihydricphenol and an aromatic dicarboxylic acid.

A particularly desirable dihydric phenol is of the following formula:##STR19## wherein Y is selected from alkyl groups of 1 to 4 carbonatoms, chlorine or bromine, z has a value of from 0 to 4, inclusive, andR' is a divalent saturated aliphatic hydrocarbon radical, particularlyalkylene and alkylidene radicals having from 1 to 3 carbon atoms, andcycloalkylene radicals having up to and including 9 carbon atoms. Thepreferred dihydric phenol is Bisphenol-A. The dihydric phenols may beused individually or in combination.

Additionally, said dihydric phenols can be used in combination with adihydric phenol of the following formula: ##STR20## wherein Y and z areas previously defined.

Suitable aromatic dicarboxylic acids include terephthalic acid,isophthalic acid, naphthalene dicarboxylic acids, and mixtures thereof,as well as alkyl substituted homologs of these carboxylic acids whereinthe alkyl groups contain from 1 to about 4 carbon atoms, and acidscontaining other inert substituents such as halides, alkyl or arylethers, and the like.

The polyarylates contain from about 95 to 0 mole percent of terephthalicacid and from about 5 to 100 mole percent of isopthalic acid. Morepreferably, the polyarylates contain a mixture of from about 25 to about75 mole percent of terephthalic acid and from about 75 to about 25 molepercent of isophthalic acid. A polyarylate containing a mixture of 50mole percent of terephthalic acid and 50 mole percent of isophthalicacid is most preferred.

The polyarylates of the present invention can be prepared by any of thewell-known prior art polyester forming reactions, such as the reactionof the acid chlorides of the aromatic dicarboxylic acids with thedihydric phenol, the reaction of the diaryl esters of the aromaticdicarboxylic acids with the dihydric phenols, and the reaction of thearomatic diacids with diester derivatives of the dihydric phenol. Theseprocesses are described in, for example, U.S. Pat. Nos. 3,317,464;3,948,856; 3,780,148; 3,824,213 and 3,133,898.

J. Other Polyesters

Other polyesters which are suitable for use herein are derived from analiphatic or cycloaliphatic diol, or mixtures thereof, containing from 2to about 10 carbon atoms and at least one aromatic dicarboxylic acid.The polyesters which are derived from an aliphatic diol and an aromaticdicarboxylic acid have repeating units of the following general formula:##STR21## wherein n is an integer of from 2 to 4. Desirably these otherpolyesters do not contain the isosorbide moiety. However, blends ofdifferent polyesters both containing an isosorbide moiety arecontemplated. Also contemplated are the polyesters described incopending application Ser. No. 09/064,720.

The preferred polyester is poly(ethylene terephthalate).

Also contemplated herein are the above polyesters with minor amounts,e.g., from 0.5 to about 2 percent by weight, of units derived fromaliphatic acids and/or aliphatic polyols, to form copolyesters. Thealiphatic polyols include glycols such as poly(ethylene glycol). Thesecan be made following the teachings of, for example, U.S. Pat. Nos.2,465,319 and 3,047,539.

Among the units which can be present in the copolyesters are thosederived from aliphatic dicarboxylic acids, e.g., of up to about 50carbon atoms, including cycloaliphatic straight and branched chainacids, such as adipic acid, cyclohexanediacetic acid, dimerized C₁₆ -C₁₈unsaturated acids (which have 32 to 36 carbon atoms), trimerized acids,and the like. In addition, there can be minor amounts of units derivedfrom aliphatic glycols and polyols, e.g., of up to about 50 carbon atomsinclude, among others, propylene glycol, glycerol, diethylene glycol,triethylene glycol and the like.

The polyesters which are derived from a cycloaliphatic diol and anaromatic dicarboxylic acid are prepared by condensing either the cis- ortrans-isomer (or mixtures thereof) of, for example,1,4-cyclohexanedimethanol with the aromatic dicarboxylic acid so as toproduce a polyester having recurring units having the following formula:##STR22##

wherein the cyclohexane ring is selected from the cis- and trans-isomersthereof and R represents an aryl radical containing 6 to 20 carbon atomsand which is the dicarboxylated residue derived from an aromaticdicarboxylic acid.

Examples of aromatic dicarboxylic acids indicated by R in formula II,include isophthalic or terephthalic acid, 1,2-di(p-carboxyphenyl)ethane,4,4'-dicarboxydiphenyl ether, etc., and mixtures of these. All of theseacids contain at least one aromatic nucleus. Fused rings can also bepresent such as in 1,4- or 1,5- or 2,6- or 2,7-naphthalene-dicarboxylicacids. The preferred dicarboxylic acid is terephthalic acid or mixturesof terephthalic and isophthalic acid.

A preferred polyester may be derived from the reaction of either thecis- or trans-isomer (or a mixture thereof) of 1,4-cyclohexanedimethanolwith a mixture of iso- and terephthalic acids. These polyesters haverepeating units of the formula: ##STR23##

Another preferred polyester is a copolyester derived from a cyclohexanedimethanol, an alkylene glycol and an aromatic dicarboxylic acid. Thesecopolyesters are prepared by condensing either the cis- or trans-isomer(or mixtures thereof of, for example, 1,4-cyclohexanedimethanol and analkylene glycol with an aromatic dicarboxylic acid so as to produce acopolyester having repeating units of the following formula: ##STR24##wherein the cyclohexane ring is selected from the cis- and trans-isomersthereof, R is as previously defined, n is an integer of 2 to 4, the xunits comprise from about 1 0 to about 90 percent by weight and the yunits comprise from about IO to about 90 percent by weight.

The preferred copolyester may be derived from the reaction of either thecis- or trans-isomer (or mixtures thereof) of 1,4-cyclohexanedimethanoland ethylene glycol with terephthalic acid in a molar ratio of 1:2:3.These copolyesters have repeating units of the following formula:##STR25## wherein x and y are as previously defined.

Polymer Blends

The polyester polymer of the present invention is desirably used inamounts of from about 5 to about 95, preferably from about 40 to about60 weight percent even more desirably from about 45 to about 55 weightpercent. The exact composition and amounts of the various components aredependent mainly on the desired product.

The compositions of this invention are prepared by any conventionalmixing methods. A preferred method includes mixing the polyester andthermoplastic polymer or mixtures thereof in powder or granular form inan extruder and extruding the mixture into strands, chopping the strandsinto pellets and molding the pellets into the desired article.

Additives

It should, of course, be apparent to those skilled in the art that otheradditives may be included in the present compositions. These additivesinclude plasticizers; pigments; flame retardant additives, particularly,decabromodiphenyl ether and triarylphosphates, such astriphenylphosphate; reinforcing agents, such as glass fibers; thermalstabilizers; ultraviolet light stabilizers; processing aids; impactmodifiers; flow enhancing additives; nucleating agents to increasecrystallinity; and the like. Other possible additives include polymericadditives such as ionomers, liquid crystal polymers, fluoropolymers,olefins including cyclic olefins, polyamides and ethylene vinyl acetatecopolymers.

This invention is further illustrated by the following non-limitingexamples.

EXAMPLES

This section dscribes the synthesis of polymers used to make blends withpolycarbonate, polybutyleneterephthalate(PBT), reinforcing glass fibers,core shell elastomers for toughening and nucleating agents forincreasing crystallinity and heat deflection temperatures.

The polymer molecular weights are estimated based on inherent viscosity(I.V.), which is measured for a 1% solution (wt./volume) of polymer ino-chlorophenol at a temperature of 25° C. The levels of catalystcomponents are expressed as ppm, based on a comparison of the weight ofthe metal with the weight of either the dimethyl terephthalate orterephthalic acid, depending on which monomer is used.

Example 1

The following polymerization reactants are added to a 50 gal. maximumcapacity, Hastalloy B polymerization reactor fitted with a 6" radius,Hastalloy B, water cooled reflux column packed with stainless steelrings, a stainless steel helix agitator stirrer, a water-cooledcondenser and by-pass: dimethyl terephthalate (78.02 kg), isosorbide(15.42 kg), and ethylene glycol (49.90 kg), which corresponds to a moleratio of 1: 0.26: 2.00. The catalyst is also charged and consists ofMn(II) acetate tetrahydrate (29.57 g), Co(II) acetate tetrahydrate(21.43 g), and Sb(III) oxide (35.02 g). This corresponds to 85 ppmmanganese (weight of metal as a fraction of the weight of dimethylterephthalate), 90 ppm cobalt, and 375 ppm antimony. The stirred reactor(50 rpm) is purged with a stream of nitrogen while the temperature israised to 250° C. over a period of four hours. The reactor is jackettedand uses a temperature controlled, hot oil loop system as a heatingmedium. Methanol is continuously collected as the reaction is heatedabove approximately 150° C. By noting when the temperature drops at thetop of the packed reflux column it is possible to determine the end ofmethanol evolution, indicating the finish of the first step of thereaction, which is the transesterification of the diols and dimethylterephthalate. At this point, 77 ppm of phosphorous is added in the formof a polyphosporic acid solution in ethylene glycol. In this case, 153ml of the solution, which has a concentration of 10.91 g phosphorous per100 g of polyphosphoric acid solution is used. Also at this time, thenitrogen purge is stopped. Heating is continued. The reaction is heatedto 285° C. over a period of about 2 hours. Vacuum is then graduallyapplied using a multi-vane vacuum pump with 20 horse-power blower. Theattainment of full vacuum, preferably less than 1 Torr, takesapproximately 1 hour. During this time, ethylene glycol distills off,and a low molecular weight polymer forms. The molten polymer is heatedunder vacuum at 285° C. for about 2 hours, until the polymer achievessufficient melt viscosity, as determined by an increase in torque of thestirrer. When sufficient viscosity is achieved, the polymerization isstopped, and the reactor is emptied through a heated die at the bottom.The molten polymer emerges as a strand that when cooled throughimmersion in a cold water trough can be chopped into pellets. Thepolymer pellets are dried overnight in a rotating drum heated to 120° C.

The cooled polymer is removed from the flask and ground. The solutioninherent viscosity (I.V.) of the material is 0.64 dL/g.

The monomer unit composition of the polymer, determined by proton NMR,is about 6% isosorbide, 42% ethylene gylcol, 2% diethylene glycol, and50% terephthalic acid, all expressed as a mole % of the polymer. It isnoteworthy that the amount of isosorbide in the polymer is approximatelyhalf of the amount that is charged, when compared with the amount ofterephthalic acid. Unreacted isosorbide is found in the distillates,especially in the ethylene glycol. The amount of isosorbide in thepolymer by this process thus is very dependent on the efficiency of thedistillation or other separation methods that are used in the process. Askilled practitioner can readily establish specific process detailsaccording to the characteristics of the reactor, distillation columns,and the like.

Example 2

The second example is prepared in a way similar to the first except thata smaller reactor (5 gal. maximum capacity) is used. The reagentequivalent ratios are also changed in order to prepare a polymer with agreater content of isosorbide. Thus, dimethyl terephthalate (10,680 g),isosorbide (5,787 g), and ethylene glycol (4,881 g), which correspondsto a mole ratio of 1:0.72:1.43 are charged to the reactor in a similarfashion as before along with the catalyst consisting of Mn(II) acetatetetrahydrate (4.76 g), and Ge(IV) oxide (4.66 g). This corresponds to100 ppm manganese (weight of metal as a fraction of the weight ofdimethyl terephthalate) and 300 ppm germanium. The germanium oxide isadded in the form of a solution in ethylene glycol (0.100 N GeO₂ inethylene glycol). A solution of polyphosphoric acid in ethylene glycolis added in a similar way as before, in this case 9.6 ml, which has aconcentration of 3.45 g P per 100 ml of polyphosphoric acid solution, isused. The polymerization proceeded in a similar fashion as before,however, the resultant finished resin did not achieve the same inherentviscosity within the given time. In this case a solution I.V. of 0.42dL/g is observed. It was also observed that the monomer unit compositionof the polymer, determined by proton NMR, is about 13% isosorbide, 34%ethylene gylcol, 3% diethylene glycol, and 50% terephthalic acid, allexpressed as a mole % of the polymer. The extent of isosorbideincorporation is somewhat lower in this case than previously observedbut reflects the efficiency of the differing reactors rather than thepolymer made.

Example 3

The third example is prepared in a way similar to the first except thata larger reactor (100 gal) equipped with a stainless steel anchor typestirrer is used. The monomers charged are such that an isosorbidecontent in the finished polymer would be 1 mole %, assuming that some ofthe input isosorbide would be distilled off during polymerization. Assuch, dimethyl terephthalate (197 kg),isosorbide (5.12 kg), and ethyleneglycol (135 kg) along with the catalysts: Mn(II) acetate tetrahydrate(72.1 g), Co(II) acetate tetrahydrate (54.1 g) and Sb(III) oxide (88.5g) are used. This corresponds to 82 ppm manganese, 65 ppm Co, and 375ppm Sb calculated using the same basis as in example 1. Thetransesterification process is carried in an analogous way as forexample 1. A polyphosphoric acid solution in ethylene glycol is addedsuch that 80 ppm of P is used to sequester the transition metals afterthe transesterification step and before the polycondensation as outlinedin Example 1. The polycondensation is also similar to the previousexample. Polymer is extruded and pelletized to give clear, colorlessresin.

Unlike the previous example, the resin produced with lower isosorbidecontent can be solid-state polymerized. The pelletized polymer is loadedinto a tumble dryer and under a stream of nitrogen is heated to 115° C.over a period of 4 hours and then held at that temperature for another 6hours. This allows the polymer to partially crystallize. After thistreatment, a vacuum is applied to the tumble dryer ulitmately achievinga vacuum less than 1 mm of Hg. The heating is continued and reaches amaximum of 213° C. It is then held at this elevated temperature for atotal of approximately 15 hours. This effects a solid-statepolymerization and allows the molecular weight to be significantlyincreased, as judged by the inherent viscosity (I.V.) of the polymersolution in ortho-chlorophenol. The solution I.V. of the materialincreases from about 0.5 dL/g to about 0.7 dL/g during the solid statepolymerization.

Example 4

This polymer is prepared in a similar way to that for example 3 exceptthat the amounts of diols were changed in order to result in a resinwith a somewhat increased isosorbide content. Thus, the only alterationsare in the amount of isosorbide charged, 17.8 kg, and the amount ofMn(II) acetate tetrahydrate catalyst used, 79.2 g corresponding to 90ppm Mn(II) calculated on the same basis as in the above example. Thetransesterification and polycondensation are repeated as has been justdescribed. Also, the finished polymer is pelletized, crystallized, andsolid-state polymerized in an identical fashion to the previous example.This results in a polymer with approximately 3 mole % isosorbidecontent.

Example 5

This example describes a blend of isosorbide containing polymer withpolycarbonate. A polymer made by Example 2 is blended with polycarbonateto make a tougher material while maintaining contact opticaltransparency. The polycarbonate is obtained from Dow Chemical(Caliber302) and blended with polymer of Example 2 in a Leistritz brand extruder(Model MC18GG/GL, Leistritz AG). The design of the twin screws consistsof conveying elements, 3 kneading blocks and then additional conveyingelements. The ratio of the length L to diameter D is 30 . The barreltemperature is 260° C. and the screw rotation speed is 225 rpm. Theextrudate is pelletized, dried overnight and molded into tensile andflexure bars for mechanical testing. The molding machine is an ArburgAllrounder (Model 220 M) made by Arburg Maschinen Fabrik(Lossburg,Germany). The molding conditions are: barrel temperature 280° C., themold temperature 50° C., screw speed 210 rpm, injection pressure 25 bar,cool time 25 seconds. The composition and physical properties of theblends are shown in Table 1. The optical haze of the blends is measuredon a flexure bar with a Macbeth Color Eye 7000 (Kollmorgen Instruments)according to ASTM D1003 (published by the American Society of TestingMaterials, Philadelphia, Pa., Vol. 8.01). The molded samples havecontact transparency.

                                      TABLE 1                                     __________________________________________________________________________    Composition (wt %) Example 5A                                                                           Example 5B                                                                          Example 5C                                    __________________________________________________________________________    Polycarb calibre   80     50    20                                              302(%)                                                                        PEIT-13(%)  20 50 80                                                          ASTM method                                                                   D638 tensile modulus na 0.34 na                                                (MPSI)                                                                       D638 tens. elong @ bk(%) na 118  na                                           D638 ten stress @ bk(ksi) na  7.3 na                                          D638 tens. elon @ yld(%) na  6 na                                             D638 tens. stress @ na  9 na                                                   yld(ksi)                                                                     D256 Notched Izod(ft-lb) 3.1 1.53 0.63                                         @ 20° C.                                                              D648 HDT(° C.)(264 psi) 1.16 101  91                                   D1746 Total Optical na 80 na                                                   transmission(%)                                                              D1003 Haze(%) na 78 na                                                      __________________________________________________________________________     na: not available                                                        

Example 6

This example describes a blend of isosorbide containing polymerstogether with PBT and core shell elastomer for toughening the blend. Thepolymer of example 1 (PEIT-6) is blended with PBT (Celanex 1600)obtained from Hoechst Ticona(Summit, N.J.) and core shell elastomersE920 obtained from Kanake (Kanake Texas Corporation, Houston, Tex.). ina Leistritz extruder as in Example 5. The samples are injection moldedand tested for mechanical properties using the same procedures outlinedin Example 5. The compositions and the mechanical results are shown inTable 2.

                  TABLE 2                                                         ______________________________________                                                                    Example                                             Composition (wt %) 6                                                        ______________________________________                                        PBT (Celanex 1600) (%)          60                                              PEIT-6 (%)  20                                                                Kanake E920 (%)  20                                                           ASTM method                                                                   D638 tensile modulus (MPSI) 0.253                                             D638 ten. elong @ bk (%) 230                                                  D638 ten stress @ bk (ksi) 4.7                                                D638 ten. elon @ yld (%) 3.63                                                 D638 ten. stress @ yld (ksi) 5.36                                             D790 flex. mod (MPSI) 0.29                                                    d790 flex stress @ bk (ksi) 0                                                 D790 flex @ 5% strain (ksi) 9.43                                              D256 Notched Izod (ft-lb) @ 20° C. nb*                                 D256 Notched Izod (ft-lb) @ -20 C. 2.28                                       D256 Notched Izod (ft-lb) @ 40 C. 1.42                                        D648 HDT (° C.) (264 psi) 52                                           D3763 multiaxial impact load (lb) @ 747                                        max. load 20° C.                                                      D3763 multiaxial impact load (lb) @ 1112                                       max. load -20° C.                                                     D3763 multiaxial impact load (lb) @ 1203                                       max. load -40° C.                                                   ______________________________________                                         *nb: no break                                                            

Example 7

This example describes a blend of isosorbide containing polymerstogether with PBT and glass fiber. The glass fiber stiffens andincreases the modulus of the blend. The polymer of example 1 (PEIT-6) isblended with PBT (Celanex 1600) obtained from Hoechst Ticona(Summit,N.J.) and glass fiber OCF 183(PPG, Pittsburgh, Pa.) in a Leistritzextruder as in example 5. The samples are injection molded and testedfor mechanical properties using the same procedures outlined in example5. The compositions and the mechanical results are shown in Table 3.

                  TABLE 3                                                         ______________________________________                                        Compos-                Exam-    Exam-                                           ition (wt %) ple 7a ple 7b                                                  ______________________________________                                        PBT celanex                60       45                                          1600 (%)                                                                      PEIT-6 (%)  10 25                                                             Glass Fiber  30 30                                                            (OCF 183) (%)                                                                 ASTM method                                                                   D638 tensile modulus (MPSI) 1.31 1.32                                         D638 ten. elong @ bk (%) 2.42 2.44                                            D638 ten stress @ bk (ksi) 17.5 17.3                                          D638 ten. elon @ yld (%) 0 0                                                  D638 ten. stress @ yld (ksi) 0 0                                              D790 flex. mod (MPSI) 1.23 1.19                                               d790 flex stress @ bk (ksi) 26.5 24.8                                         D790 flex @ 5% strain (ksi) 0 0                                               D256 Notched Izod (ft-lb) @ 20° C. 1.69 1.81                           D648 HDT(° C.) (264 psi) 90 87                                         D3763 multiaxial impact load (lb) @ 275 292                                    max. load 20° C.                                                      D3763 multiaxial impact load (lb) @ 311 306                                    max. load -20° C.                                                     D3763 multiaxial impact load (lb) @ 285 315                                    max. load -40° C.                                                   ______________________________________                                    

It is to be understood that the above described embodiments areillustrative only and that modification throughout may occur to oneskilled in the art. Accordingly, this invention is not to be regarded aslimited to the embodiments disclosed herein.

What is claimed is:
 1. A polymer blend comprising (1) a polyestercomprising terephthaloyl moieties and, optionally, other aromatic diacidmoieties; ethylene glycol moieties; diethylene glycol moieties whereinsaid diethylene glycol moieties are present in an amount of at leastabout 0.25 mole % of the polyester; isosorbide moieties, and,optionally, one or more other diol moieties, wherein said polyester hasan inherent viscosity of at least about 0.35 dL/g when measured as a 1%(weight/volume) solution of said polyester in o-chlorophenol at atemperature of 25° C., and (2) another thermoplastic polymer.
 2. Thepolymer blend according to claim 1, wherein said another thermoplasticpolymer is selected from the group consisting of polycarbonates, styreneresins, alkyl acrylate resins, polyurethane resins, vinyl chloridepolymers, polyarylethers, copolyetheresters, polyhydroxyethers,polarylates, and other polyesters.
 3. The polymer blend according toclaim 1, wherein said polyester comprises about 40% to about 50%terephthaloyl moieties and a total of up to about 10 mole % of one ormore optional other aromatic diacid moieties.
 4. The polymer blendaccording to claim 3, wherein said terephthaloyl moieties are derivedfrom terephthalic acid or dimethyl terephthalate.
 5. The polymer blendaccording to claim 3, wherein said ethylene glycol moieties are presentin an amount of about 10 mole % to about 49.5 mole % of the polyester,said diethylene glycol moieties are present in the amount of about 0.25mole % to about 10 mole % of the polyester, said isosorbide moieties arepresent in an amount of about 0.25 mole % to about 40 mole % of thepolyester, and said one or more other diol moieties are present in anamount of up to about 15 mole % of the polyester.
 6. The polymer blendaccording to claim 1, wherein said one or more other diol moieties arederived from aliphatic alkylene glycols or branched aliphatic glycolshaving from 3-12 carbon atoms and having the empirical formula HO--C_(n)H_(2n) --OH, where n is an integer from 3-12; cis ortrans-1,4-cyclohexanedimethanol or mixtures thereof; triethylene glycol;2,2-bis[4-(2-hydroxyethoxy)phenyl]propane;1,1-bis[4-(2-hydroxyethoxy)-phenyl]cyclohexane;9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene; 1,4:3,6-dianhydromannitol;1,4:3,6-dianhydroiditol; or 1,4-anhydroerythritol.
 7. The polyesterblend according to claim 1, wherein said optional other aromatic diacidmoieties are derived from isophthalic acid, 2,5-furandicarboxylic acid,2,5-thiophenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,2,7-naphthalenedicarboxylic acid, or 4,4'-bibenzoic acid.
 8. Thepolyester blend according to claim 1, wherein terephthaloyl moieties arepresent in an amount of about 45 mole % to about 50 mole % of saidpolyester, said optional other aromatic diacid moieties are present inan amount up to about 5 mole % of said polyester, said ethylene glycolmoieties are present in an amount of about 10 mole % to about 49.5 mole% of said polyester, said diethylene glycol moieties are present in anamount of about 0.25 mole % to about 5 mole % of said polyester, saidisosorbide moieties are present in an amount of about 0.25 mole % toabout 30 mole % of said polyester, and said other diol moieties arepresent in an amount of up to about 10 mole % of said polyester.
 9. Thepolyester blend according to claim 8, wherein said other diol moietiesare derived from cis-1,4-cyclohexanedimethanol,trans-1,4-cyclohexanedimethanol, or mixtures thereof.
 10. The polyesterblend according to claim 9, wherein said optional other aromatic diacidmoieties are derived from isophthalic acid, 2,6-naphthalenedicarboxylicacid, 4,4'-bibenzoic acid, or mixtures thereof.
 11. The polyester blendaccording to claim 1, wherein said polyester has an inherent viscosityof at least about 0.50 dL/g.
 12. The polyester blend according to claim10, wherein said polyester has an inherent viscosity of at least about0.65 dL/g.